Germicidal compositions



United States Patent 3,380,923 GERMICIDAL CGB/iPOSiTlUNS Martin D.Beach, London, England, assignor to Whitmoyer-Reed Limited, Barking,Essex, Engiand, a British company No Drawing. Filed Nov. 15, 1965, Ser.No. 507,666 Claims priority, application Great Britain, Nov. 16, 1964,46,499/64 7 Claims. (Cl. 252-106) ABSTRACT OF THE DISCLOSURE Disclosedherein are certain germicidal detergent compositions, and particularly,iodophors wherein the iodine carrier is an alkylene oxide condensatehaving amphoteric properties. Such germicides are especially suitablefor the poultry and dairy industry.

This invention is concerned with germicidal detergent compositions,including compositions known as iodophors, an iodophor being acom-position containing iodine and a carrier in which the carrier is acompound which increases the solubility of iodine in aqueous systems.

In an iodophor, the iodine is apparently chemically bound to, and/ orcomplexed with, the carrier.

Among the known iodophors are those comprising iodine and a surfactant.To form germicidal compositions, these iodophors are frequentlyformulated with phosphoric acid to yield aqueous concentrates which arefinally diluted with water by the end-user.

A most important characteristic of iodophors in their dilutedready-to-use form is that they should possess a low iodine vapourpressure combined with a high and constant available iodine content, bywhich is meant that at least 50% of the total iodine present should betitratable with thiosulphate solution and that this titratable quantityshould remain constant over a period of time.

It has now been found that iodophors which possess the abovecharacteristics to a marked degree in comparison with many iodophorsbased on conventional surfactants, such as non-ionic surfactants, can bemade by using a surfactant having amphoteric properties.

Based on the above discovery, the present invention provides agermicidal detergent composition containing iodine and a water-solubleamphoteric surfactant. The composition is preferably in the form of ahomogeneous liquid or semi-solid solution which advantageously is anaqueous solution also containing phosphoric acid. The compositions maycontain one or more additional nonamphoteric, e.g., anionic ornon-ionic, surfactants if these are required to confer additionaldetergency or to act as clarifying agents if the composition in theirdiluted form should show a tendency towards cloudiness. A low molecularweight alcohol such as isopropyl alcohol may also be included as aclarifying agent.

Whilst many amphoteric surfactants can be used, those preferred arealkylene oxide condensates containing groups which impart amphotericproperties, e.g., amine and sulfate groups. Examples of suchsurfactants, which have been found to be of special utility, are thosecomprising mixtures of compounds of the formula:

where R R and R are alkyl groups containing a total of 7 to 24 carbonatoms, R, is hydrogen or C -C alkyl, particularly methyl, m is aninteger and X is hydrogen or 3,380,923 Patented Apr. 30, 1968 an alkalimetal, preferably sodium, the mixture containing an average of 6-100,and preferably 12-50 groups per molecule. Preferably, compounds of theabove formula are ethylene oxide derivatives in which case R, will behydrogen exclusively; but the compounds may be derived from otheralkylene oxides, e. g. mixtures of ethylene and propylene oxides. It isalso preferred that compounds of the above formula be derived fromisomeric mixtures of amines of the formula ial Rn-Cf-NH:

and which contain 12 to 24 carbon atoms, e.g. mixtures of aminescontaining 12 to 15 carbon atoms or 18 to 24 carbon atoms. Surfactantsof the class just described are of particular utility in formingready-for-use germicidal compositions of low iodine vapour pressurecombined with a high and constant available iodine content.

Other usable amphoteric surfactants are those of the classes set forthbelow:

1) Amino-substituted alkanoic acids and salts thereof, such as thosecontaining from 2 to about 8 carbon atoms in the alkanoic acid portionand having as a substituent an amino group whose remaining two valencesare satisfied by hydrogen and a C3-C18 hydrocarbon or acyl group. Atypical sub-class of such compounds is represented by the formula:

where R represents a surface activity producing group with 8 to 18 ormore carbon atoms and M is a salt-forming cation or hydrogen.

(2) Betaine type of compounds such as betaine derivatives of theformula:

where R is as defined above and R R and R are shorter chain alkyl (oralkylene in the case of R groups, e.g. methyl or methylene.

(3) Compounds having the formula:

R N(CH CH O OM 2 where R is as defined above and M is a salt-formingcation or hydrogen.

In general, the weight ratio of amphoteric surfactant to iodine willrange from 1:1 to 50:1, and preferably ranges from 2:1 to 10: 1. Theamount of iodine in a concentrate intended to be diluted by the end-userwill gen erally be from 0.5 to 6% by weight, preferably 1 to 3% and theamount of amphoteric surfactant in this type of composition willgenerally range from 2 to 25% by weight.

When, as is preferred, phosphoric acid is present, concentrates fordilution with water by the end-user will generally contain theequivalent of about 2 to 5 0% by Weight, typically 4 to 30% by weight,phosphoric acid.

If a non-amphoteric surfactant is included in the composition suchsurfactant may be one of the conventional non-ionic materials such ascondensates of an alkylene oxide, e.g., ethylene and/ or propyleneoxide, and a hydrophobic compound containing an active hydrogen atom.Preferred non-ionic surfactants are condensates of octyl or nonyl phenoland 6 to moles of ethylene oxide. Alternatively there may be usedanionic surfactants such as sulfonated or sulfated materials.

3 The invention is illustrated by the following examples in whichSurfactants A-F are those identified below:

Surfactant A is a mixture of amphoteric compounds of the formula:

residues are derived from a commercial mixture of isomeric amines having12-15 carbon atoms and exhibiting a tertiary alkyl structure at thepoint of attachment to the amino nitrogen atom and m is an integer;there being an average of 15 CH CH O- groups per mole of amphotericcompound.

Surfactant B is a non-ionic condensate of otcylphenol and 9-10 moles ofethylene oxide.

Surfactant C is a product available commercially as Ambiteric D fromGlovers (Chemicals) Ltd, Leeds, England; it is believed to consistpredominantly (=8590%) of molecules of the formula:

R B1-NR3CO0- R4 where R represents long chain alkyl, at least 90% ofsuch alkyl radicals being dodecyl, R and R are methyl and R ismethylene.

Surfactant D is a product available as Ambiteric H and is similar toAmbiteric D described above except that at least 90% of the R alkylradicals are hexadecyl.

Surfactant E is a product available commercially as Deriphat 1700 fromGeneral Mills, Inc., Illinois, United States of America. This productcontains ca. 50% N- lauryl myristyl B-aminopropionic acid.

Surfactant F is a product available commercially as Empigen BB fromMarchon Products Ltd, Whitehaven, England; it contains 30% activeingredient which is similar to the active component in Surfactant Cdescribed above except that the R radicals are predominantlylauryl/myristyl.

In the examples which now follow parts and percentages are on a weightbasis and in all instances the iodophors described were made by mixingthe iodine'and the amphoteric surfactant at a temperature of 35 C. andfor a sufiicient time to result in the iodophor.

Example I There are intimately mixed 3.5 parts of iodine and 20 parts ofSurfactant A to form a homogeneous iodophor which can be formulated intoa germicidal concentrate for the dairy and poultry industries.

Example 11 23.5 parts of the iodophor of Example I are mixed with 50parts of phosphoric acid (85%) and water is added to make 125 parts. Theproduct on dilution with water forms an excellent germicidal detergentwhich passes the test described by Hoy et al. in the Journal of AppliedBacteriology 23 (2), pp. 359-371 and which is therefore.

particularly suited for use in the diary industry.

Example III There are intimately mixed 3.5 parts of iodine and parts ofSurfactant A. To the iodophor thus made are 4 added 5 parts phosphoricacid 7 parts of Surfactant B and water to make a total of parts. Thereresults a germicidal detergent composition suitable for use in thepoultry industry after suitable dilution with water.

Example V There are intimately mixed 3.5 parts of iodine and 10 parts ofSurfactant A and to the iodophor thus obtained there are added 50 partsphosphoric acid (85 7 parts of Surfactant B and water to make 100 parts.There results a germicidal detergent composition useful in the dairyindustry after dilution with water.

Example VI (a) There are intimately mixed 3.5 parts of iodine and 12parts of Surfactant C to form an iodophor. There are then added 5 partsof phosphoric acid (85%), 12 parts of Surfactant B and water to makeparts. The product is suitable as a germicide for the poultry industryafter dilution with water.

(b) Part (a) is repeated except that Surfactant C is replaced by thesame quantity of Surfactant D, 10 parts of the water is replaced by 10parts of isopropyl alcohol and an additional 8 parts of Surfactant B areadded.

(0) Part (a) is repeated except that an additional 45 parts ofphosphoric acid (85%) are added. The product is suitable for the dairyindustry after dilution.

Example VII (a) There are intimately mixed 5 parts of iodine and 30parts of Surfactant E to form an iodophor. There are then added 7.5parts of phosphoric acid (85% 20 parts of Surfactant B and water to makeparts. The product is a germicide suitable for use in the poultryindustry.

(b) Part (a) is repeated except that 75 parts of phosphoric acid (85 areadded and water is added to make 200 parts. The product is suitable foruse in the dairy industry after dilution with water.

Example VIII (a) There are intimately mixed 5 parts of iodine and 45parts of Surfactant F to form an iodophor. To the iodophor are added 7.5parts of phosphoric acid (85 20 parts of Surfacant B, 10 parts isopropylalcohol and water to make 180 parts. The product is suitable for use inthe poultry industry.

(b) Part (a) is repeated except that 75 parts of phosphoric acid (85%)are used and water is added to make 210 parts. The product is useful inthe dairy industry after dilution with water.

I claim:

1. An iodophor composition consisting essentially of iodine and, aswater-soluble amphoteric surfactant, a mixture of compounds of theformula:

where R R and R are alkyl groups containing a total of 7 to 24 carbonatoms, R; is selected from the group consisting of hydrogen and alkylgroups having 1 to 4 carbon atoms, m is an integer having an averagevalue of 6 to 100 and X is selected from the group consisting ofhydrogen and the alkalimetals, the weight ratio of surfactant to iodineranging from 1:1 to 50:1.

2. A composition according to claim 1, wherein R is hydrogen, X issodium and the mixture contains an average of 12 to 50 -(CH CH O)-groups per molecule.

3. A composition according to claim 1; wherein the weight ratio ofsurfactant to iodine is from 2:1 to 10:1.

4. A concentrate for dilution with water to form a germicidal detergentcomposition which consists essentially of iodine, phosphoric acid and,as amphoteric surfactant, a mixture of compounds of the formula:

where R R and R are alkyl groups containing a total 5 of 7 to 24 carbonatoms, R; is selected from the group consisting of hydrogen and alkylgroups having from 1 to 4 carbon atoms, m is an integer having anaverage value of 6 to 100 and X is selected from the group consisting ofhydrogen and the alkali metals, the weight ratio of surfactant to iodineranging from 1:1 to 50:1.

5. A concentrate according to claim 4 which contains 0.5 to 6% by weightof iodine and wherein the weight ratio of surfactant to iodine is from2:1 to 10:1.

6. A concentrate according to claim 4 which contains the equivalent of 2to 50% by weight of 85% phosphoric acid.

7. A concentrate according to claim 4 which also contains a nonionicsurfactant comprising a condensate of an alkylene oxide and ahydrophobic compound containing an active hydrogen atom.

References Cited UNITED STATES PATENTS 3,291,692 12/1966 Hagerty 2521073,277,010 10/1966 Schenck et a1. 252l06 LEON D. ROSDOL, PrimaryExaminer.

S. E. DARDEN, S. D. SCHNEIDER,

Assistant Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,380,923 April 50 1968 Martin D. Beach It is certified that error appears inthe above identified patent and that said Letters Patent are herebycorrected as shown below:

Column 2, lines 32 and 33, the formula should appear as shown below:

R N(CH CH COOM) Column 3, lines 26 to 29, the formula should appear asshown below:

Signed and sealed this 16th day of December 1969.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR. Attesting OfficerCommissioner of Patents

